Azo-dyestuffs insoluble in water



2,937,166 AZO-DYESTUFFS INSOLUBLE IN WATER Herbert Kracker, Hans Albert, and Walter Staab, all of Olfenba'ch 'am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormal's Meister Lucius &

Bruning, Frankfurt am Main, Germany, a corporation of Germany No'Drawing. Application July 1, 1958 Serial No. 745,819 Claims priority, application Germany July 6, 1957 6 Claims. (Cl. arso -15s The present invention relates to new azo-dyestufis insoluble in water and to a process for preparing the same; more particularly it relates to dyestuffs corresponding to the following general formula represents an alkyl or ai'yl radical and 'R" stands for an aromatic orfheterocyclic radical free from groups imparting solubility in water.

wherein X represents an alkyl or alkoxy group, R I

In U.S.'-pate'n' t application Serial No. -667,96'1,'.filed June 25, 1957, in the-name of Herbert Kracker and Hans Albert is disclosed a process for the manufacture ofazodyestuffs insoluble in water, wherein thediazonium compound from an ortho-amino-azo compound of the general formula Gram-Oman SO:.alkyl NE: in which :X" represents an alky-l or alkoxy group, is coupled in substance, on the fiber or on another substratum with an arylamide of 2,3-hydroxynaphthoic acid which is free from groups imparting solubility in water.

According to this process, greenish-brown to green dyestuffs are obtained which are distinguished by good properof fastness.

Now, we have found that dyestu'fls'of similai' good V fastness properties are obtained by coupling in substance, on the fiber or on another substratum the diazonium compound from an ortho-amino-azo compound of the general formula SOralkyl NH: in which X represents an alkyl or alkoxy group, with an arylamide of a fi-keto-carboxylic acid of the general formula in which R represents an alkyl or aryl radical and R stands'for an aromatic or heterocyclic radical free fro groups imparting solubility in water.

The new dyestuffs yield according to known dyeing and printing methods mainlygreen, brown and black tints. The process is particularly valuable for the production of insoluble azo-dyestufis by printing since, in addition to yellow and'red to claret tints, there can also be ob- 2,937,166 Patented May 17, 19cc tained green and black tints which could not be produced hitherto in practice with the use of arylamides of fl-ket'ocarboxylic acids.

The new dyestuils possess in many cases a good fastness to light and to wet-processing and represent, therefore, a valuable enrichment of the class of ice-colors.

The following examples serve to illustrate the invention but they are not intended to limit it thereto:

Example 1 Cotton fabric is padded on the foulard with the following solution:

33.8 grams of 2-acetoacetylamino-6-ethoxybenzthiazole are pasted up with 7 34 cc. of denatured alcohol,

17 ccQof warm water and 7 cc. of a sodium hydroxide solution of 38 136 and made up to 1 liter with water of 50-60 C. and

20 cc. of Monopol Brilliant oil.

The dried fabric is developed on the foulard with a solution containing per liter of water 14.7 grams of 2-amino-4,5-diethoxy-2i-methylsulfonyl-qlnitro-1,1-azobenzene in the form of a diazonium compound prepared in the usual manner,

1 gram of a reaction product from about ZO mols of ethylene oxide and 1 mol of oetodecyl alcohol, and

20 cc. of acetic acid of 50 percent strength.

SOLCHS N g S I C Ha-rC O-GH-G ONH-C O CzHi Example 2 Cotton fabric is padded on the foulardwith the following solution:

14 grams of 1-acetoacetylamino-2,5-dimethoxy-4-chlorobenzene are pasted up with 20 cc. of Monopol Brilliant oil and 10 cc. of a sodium hydroxide solution of 38 B, and the dissolved by the addition of 350 cc. of boiling water. The whole is madeup to 1 liter with cold water.

The dried fabric is printed with a printing paste containing per kilogram 14.7 grams of 2-amino-4,S-diethoxy-Z'-methylsulfonyl-4'- nitro-1,1-azobenzene in the form of a diazonium'compound prepared in the usual manner,

20 cc. of thiodiethylene glycol,

20 cc. of acetic acid of 50 percent strength,

50 grams of urea and starch tragacanth as thickening agent.

The fabric is then dried, washed with a hot sodium bisulfite solution and a hot dilute sodium carbonate solution, soaped for 20 minutes in the usual manner, rinsed and dried. A black print is obtained. The following table indicates a number of further components which can be used in this invention, and also the tints of the amdyestufis produced from the components on the fiber.

Dlazo Component Coupling Component Tint 3. The azo-dyestulf of the following fotnaula I 2 amino 4,5 diethoxy -2' 1 l acetoacetylamlno 2,5 reddish gray. methylsulfonyl 4 nitro dimethylbenzene.

1',1'-azobenzene.

Do 1-benzoy1acetylamino-2,5- reddish dark dimethoxy 4 benzoylbrown. amlnobenzene. I 2-am1no-4,5-dl-n-propoxy- 2 acetoacetylemlno 6 covered v 2-methylsulfonyl-4-nltroethoxybenzthiazole. green. i 3 -0 0-0 11-0 0 g 1,1-azobenzene.

Do 1 acetoaeetylamino 2.5 brownish Z tgimethoxy 4 chloro garnet. 0 CH; 4 I I enzene. I I D0 -a etoare yla no-zfieddi h my 4. The azo-dyestufivof the following formula duuethylbenzene. brown. I Y e v I I I Do 1-benzoy1acety1am1no-2,5- red-brown. 0C;H n

I J i I v w(llmethoxy-i-benzoyll aminobenzene.

Do l-a cetoacety lamino-2,5- gray-brown.

gimethoxy- 4 chloro S\. enzene. Do 1-acetoacetylamino-2,5- bluish H I I v dimethylbenzene. garnet. I OIL-G 0- H- OO-NH-C Do. 1-benzoylacety1amino-2,5- dark brown. dimethoxy 4 benzoyl s aminobenzene. N l 5. The azo-dyestufi of the following formula We claim: a 00H;

1. Azo-dyestufis insoluble in water corresponding to I i I I 'the following general formula O|NQN=N-OO G|H| I 1 0X 80:.CH: N

RC 0-(311-0 0-NH-R I 6. The azo-dyestufi of the following formula wherein X i epresents a lower alkyl group containing from R 1 to 3 carbon atoms, R represents a member selected from the group consisting of methyl and phenyl, and R stands QFi for a member selected from the group consistmg of 40 soacnz N radicals of the benzene and benzthiazole series. 0CH| 2. The azo-dyestuif of the following formula a f V CHr-C o-oH-c o-NH- e1 7 1 1 V i I- OgN' N=N V 02H; 7 OH.

References Cited in the file of this patent h S 'UNITED STATES PATENTS V m. 2,783,225 Langbein Feb. 26, 1957 0113-0 0-CH-C0-NH-C I N I FOREIGN PATENTS 832,179 Germany Feb. 21, 1952 

1. AZO-DYESTUFFS INSOLUBLE IN WATER CORRESPONDING TO THE FOLLOWING GENERAL FORMULA 